JPH0751607B2 - Solvent removal method for chlorinated resin - Google Patents
Solvent removal method for chlorinated resinInfo
- Publication number
- JPH0751607B2 JPH0751607B2 JP62192194A JP19219487A JPH0751607B2 JP H0751607 B2 JPH0751607 B2 JP H0751607B2 JP 62192194 A JP62192194 A JP 62192194A JP 19219487 A JP19219487 A JP 19219487A JP H0751607 B2 JPH0751607 B2 JP H0751607B2
- Authority
- JP
- Japan
- Prior art keywords
- chlorinated
- solvent
- resin
- chlorinated resin
- present
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は塩素化樹脂中に残存する溶媒の除去方法に関す
る。更に詳しくは、本発明は超臨界抽出法により塩素化
樹脂中に残存する溶媒を除去する方法に関する。TECHNICAL FIELD The present invention relates to a method for removing a solvent remaining in a chlorinated resin. More specifically, the present invention relates to a method for removing a solvent remaining in a chlorinated resin by a supercritical extraction method.
炭化水素系樹脂を塩素化して得られる塩素化樹脂は、塗
料、インキ、接着剤などに広く用いられている。これら
の塩素化樹脂は炭化水素系樹脂を溶媒中で塩素化して得
られることから、生成した塩素化樹脂中には溶媒が残存
し、これを除去する必要があった。Chlorinated resins obtained by chlorinating hydrocarbon-based resins are widely used in paints, inks, adhesives and the like. Since these chlorinated resins are obtained by chlorinating a hydrocarbon resin in a solvent, the solvent remains in the produced chlorinated resin and it was necessary to remove it.
従来かかる除去方法としては、塩素化樹脂を加熱して内
部の溶媒を飛ばす方法が一般に取られていたが、かかる
方法では溶媒を１％以下に減少させることが難しい上
に、加熱により樹脂を劣化し品質の悪い製品となるとい
う欠点があった。更に加熱のためのエネルギーもかなり
必要であり、改善の余地が多々残されていた。Conventionally, as a method for removing the chlorinated resin, a method of heating the chlorinated resin to remove the solvent inside has been generally used. However, in such a method, it is difficult to reduce the solvent to 1% or less, and the resin is deteriorated by heating. However, there was a drawback that it became a poor quality product. Furthermore, considerable energy is required for heating, and there is plenty of room for improvement.
上記問題点を改善するため、特公昭60−24801号では熱
水又は熱風加熱に赤外線加熱を組み合わせた溶媒除去方
法が提案されているが、加熱法に変わりなく、製品劣化
や効率の面で満足できるものではなかった。In order to improve the above problems, Japanese Patent Publication No. 60-24801 proposes a solvent removal method that combines infrared heating with hot water or hot air heating, but is satisfactory in terms of product deterioration and efficiency without changing to the heating method. It wasn't possible.
一方、超臨界状態にある流体は多くの物質を溶解する能
力があることは古くから知られており、これに基づいた
超臨界抽出技術は従来主に医薬品、食品、化粧品成分の
抽出に検討されていた。On the other hand, it has long been known that fluids in the supercritical state have the ability to dissolve many substances, and supercritical extraction technology based on this has been studied mainly for the extraction of pharmaceuticals, foods, and cosmetic ingredients. Was there.
本発明はこの超臨界抽出技術を塩素化樹脂の溶媒除去に
応用して、前記の問題点の解消を図るものである。The present invention is intended to solve the above-mentioned problems by applying this supercritical extraction technique to solvent removal of chlorinated resin.
即ち、本発明の塩素化樹脂の溶媒除去方法は、塩素化樹
脂中に残存する溶媒を超臨界状態の流体と接触させて除
去することを特徴とする。That is, the method for removing a solvent of a chlorinated resin of the present invention is characterized in that the solvent remaining in the chlorinated resin is contacted with a fluid in a supercritical state to be removed.
本発明の塩素化樹脂としては、ポリエチレン、ポリプロ
ピレン、ポリエチレン−ポリプロピレン共重合体、天然
ゴム、合成ゴム、ポリイソプレン、ポリブタジエン、エ
チレン−酢酸ビニル共重合体、或いはこれらの混合物な
どの樹脂を塩素化したものが挙げられ、塩素化の程度は
低塩素化物でも高塩素化物でもよく、更に樹脂中に可塑
剤、安定剤、その他の助剤を含んでいても構わない。特
に本発明の塩素化樹脂中に予め可塑剤を１〜10％添加し
ておくと溶媒除去効果は向上する。As the chlorinated resin of the present invention, a resin such as polyethylene, polypropylene, polyethylene-polypropylene copolymer, natural rubber, synthetic rubber, polyisoprene, polybutadiene, ethylene-vinyl acetate copolymer, or a mixture thereof is chlorinated. The degree of chlorination may be low chlorination or high chlorination, and the resin may further contain a plasticizer, a stabilizer and other auxiliaries. In particular, if the plasticizer is added in advance to the chlorinated resin of the present invention in an amount of 1 to 10%, the solvent removing effect is improved.
次に本発明における溶媒とは、上記塩素化樹脂の製造に
当たって用いられる、四塩化炭素、クロロホルム、塩化
メチレン、クロルエタン、ジクロルエタン、トリクロル
エタン、テトラクロルエタン、及びこれらの混合物を含
む塩素化炭化水素系溶媒である。Next, the solvent in the present invention, used in the production of the above chlorinated resin, carbon tetrachloride, chloroform, methylene chloride, chloroethane, dichloroethane, trichloroethane, tetrachloroethane, and chlorinated hydrocarbon system containing a mixture thereof. It is a solvent.
次に本発明における超臨界状態にある流体としては、二
酸化炭素、フロンなどが挙げられるが、このうち二酸化
炭素は、四塩化炭素等の溶媒及び塩素化樹脂と溶解度定
数も近く、毒性、引火性、加熱性もなく、溶媒との分離
も簡単で有利である。Next, examples of the fluid in the supercritical state in the present invention include carbon dioxide and freon. Among them, carbon dioxide has a solubility constant close to that of a solvent such as carbon tetrachloride and a chlorinated resin, and toxicity and flammability. It is advantageous because it has no heating property and can be easily separated from the solvent.
以下本発明を塩素化樹脂としては塩素化ゴム、溶媒とし
ては四塩化炭素、超臨界流体として二酸化炭素を例にし
て説明する。The present invention will be described below by taking chlorinated rubber as a chlorinated resin, carbon tetrachloride as a solvent, and carbon dioxide as a supercritical fluid.
第１図は本発明の実施を説明するフローチャートであ
る。まず超臨界状態の二酸化炭素はボンベ１からポンプ
２により、予熱器３を経て抽出槽４へ送られる。抽出槽
４内には予め脱溶媒を行うべき塩素化ゴム粉末が収容さ
れている。抽出槽４内では送られてきた超臨界状態の二
酸化炭素と塩素化ゴム粉末が混合され、塩素化ゴム中の
溶媒四塩化炭素は二酸化炭素に抽出される。四塩化炭素
を含む二酸化炭素はトラップ５へ送られ、ここで四塩化
炭素が回収された後、二酸化炭素は大気中へ解放され
る。なお、二酸化炭素は大気中解放せず、回収して再び
使用するようにしてもよい。６はガスクロマトグラフィ
ー、７はガスメーターである。FIG. 1 is a flow chart for explaining the implementation of the present invention. First, carbon dioxide in a supercritical state is sent from the cylinder 1 by the pump 2 to the extraction tank 4 via the preheater 3. The extraction tank 4 contains chlorinated rubber powder to be desolvated in advance. In the extraction tank 4, the supercritical carbon dioxide sent and the chlorinated rubber powder are mixed, and the solvent carbon tetrachloride in the chlorinated rubber is extracted into carbon dioxide. Carbon dioxide containing carbon tetrachloride is sent to trap 5, where carbon tetrachloride is recovered and then released to the atmosphere. The carbon dioxide may be recovered and used again without being released to the atmosphere. 6 is a gas chromatography and 7 is a gas meter.
抽出時の温度、圧力は、製品や溶媒の種類などによりい
ろいろな条件の選択が考えられるが、好ましくは30〜12
0℃、75〜250kg/cm2にするのがよい。The temperature and pressure during extraction may be selected under various conditions depending on the type of product or solvent, but preferably 30 to 12
It is recommended that the temperature be 0 ° C and 75 to 250 kg / cm 2 .
本発明においては塩素化樹脂を加熱劣化させることな
く、樹脂中の残存溶媒を効率的に低濃度まで除去するこ
とができるので、高品質の塩素化樹脂を得ることができ
る。In the present invention, the residual solvent in the resin can be efficiently removed to a low concentration without degrading the chlorinated resin by heating, so that a high quality chlorinated resin can be obtained.
以下本発明を実施例により更に詳しく説明するが、本発
明はこれらの実施例に限定されるものではない。Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
実 施 例 １（塩素化ゴム） ポリイソプレンラバー（平均分子量840×103）1kgを四
塩化炭素25kgに溶解し、空気にて分子量調節した後70℃
まで加熱し、窒素ガスで溶存酸素をパージし、塩素化触
媒としてアゾビスイソブチロニトリル5gを加えよく撹拌
した。次いでガス状塩素を12時間かけて吹き込み、塩素
含有量66％の塩素化ポリイソプレンを得た。この反応液
を熱水中に激しく撹拌しながら徐々に添加して白色の粉
末を得た。これを遠心脱水した後60℃で24時間乾燥した
ものは四塩化炭素を8.0％含んでいた。Example 1 (chlorinated rubber) 1 kg of polyisoprene rubber (average molecular weight 840 × 10 3 ) was dissolved in 25 kg of carbon tetrachloride, and the molecular weight was adjusted with air, then 70 ° C.
The mixture was heated to 0 ° C., dissolved oxygen was purged with nitrogen gas, 5 g of azobisisobutyronitrile as a chlorination catalyst was added, and the mixture was stirred well. Then, gaseous chlorine was blown in for 12 hours to obtain chlorinated polyisoprene having a chlorine content of 66%. The reaction solution was gradually added to hot water with vigorous stirring to obtain a white powder. The product obtained by centrifugal dehydration and then dried at 60 ° C. for 24 hours contained 8.0% of carbon tetrachloride.
この塩素化ゴムを抽出槽に50g入れ、表１に示す温度、
圧力、流量、時間で超臨界状態の二酸化炭素を送り込ん
だ。超臨界抽出後の塩素化ゴムが含有する四塩化炭素
（CTC）量は表１に示す通りであった（表１〜、
〜）。50 g of this chlorinated rubber was put in an extraction tank, and the temperature shown in Table 1
Carbon dioxide in supercritical state was sent in at pressure, flow rate and time. The amount of carbon tetrachloride (CTC) contained in the chlorinated rubber after supercritical extraction was as shown in Table 1 (Tables 1 to 1,
~).
実 施 例 ２（塩素化ポリエチレン） 実施例１と同様にして、原料にポリエチレンワックス
（平均分子量5000）を用いて、塩素含有量67％、四塩化
炭素量6.5％の塩素化ポリエチレンを得た。これを実施
例１と同様に超臨界抽出した後の塩素化ポリエチレンが
含有するCTC量を表１に示した（表１、）。Example 2 (Chlorinated Polyethylene) In the same manner as in Example 1, polyethylene wax (average molecular weight: 5000) was used as a raw material to obtain a chlorinated polyethylene having a chlorine content of 67% and a carbon tetrachloride content of 6.5%. The amount of CTC contained in the chlorinated polyethylene after supercritical extraction of this is shown in Table 1 in the same manner as in Example 1 (Table 1).
上記塩素化ゴムの脱溶媒前の色調はガードナー１〜２で
あった。超臨界抽出処理後の色調もガードナー１〜２で
変化がなかった。 The color tone of the above chlorinated rubber before desolvation was Gardner 1-2. The color tone after the supercritical extraction treatment did not change in Gardner 1-2.
これに対し、同じ塩素化ゴムを加熱法により脱溶媒した
場合、可塑剤を含まないものでは120℃,1〜２時間の加
熱でCTC量は４〜６％、ガードナー４〜５であり、可塑
剤を含むものは同様の加熱でCTC量は１〜２％、ガード
ナー７〜９であった。On the other hand, when the same chlorinated rubber was desolvated by the heating method, the one containing no plasticizer had a CTC content of 4 to 6% and Gardner 4 to 5 after heating at 120 ° C for 1 to 2 hours. With the same heating, those containing the agent had CTC amounts of 1 to 2% and Gardner 7 to 9.
また、塩素化ポリエチレンについても脱溶媒前の色調は
ガードナー１以下であり、超臨界抽出後の色調も変化な
くガードナー１以下であった。これに対し、上記と同じ
加熱法により処理したものはCTC量が２〜３％、ガード
ナー２〜３であった。Also, regarding chlorinated polyethylene, the color tone before desolvation was Gardner 1 or less, and the color tone after supercritical extraction was also Gardner 1 or less without change. On the other hand, those treated by the same heating method as above had a CTC content of 2-3% and Gardner 2-3.
本発明によれば、塩素化樹脂中に存在する塩素炭化水素
系溶媒を容易に１％以下、より好ましくは0.5％以下ま
で除去でき、しかもそれによって塩素化樹脂を劣化させ
ることがない。従って、品質優良な塩素化樹脂を効率的
に得ることができる。According to the present invention, the chlorinated hydrocarbon solvent present in the chlorinated resin can be easily removed to 1% or less, more preferably 0.5% or less, and the chlorinated resin is not deteriorated thereby. Therefore, a chlorinated resin having excellent quality can be efficiently obtained.
第１図は本発明の溶媒除去方法の工程を説明するフロー
チャートである。 １……ボンベ ２……ポンプ ３……予熱器 ４……抽出槽 ５……トラップFIG. 1 is a flow chart for explaining the steps of the solvent removal method of the present invention. 1 ... Cylinder 2 ... Pump 3 ... Preheater 4 ... Extraction tank 5 ... Trap
Claims (4)
の流体と接触させて除去することを特徴とする塩素化樹
脂の溶媒除去方法。1. A method for removing a solvent of a chlorinated resin, which comprises removing the solvent remaining in the chlorinated resin by contacting with a fluid in a supercritical state.
１項記載の溶媒除去方法。2. The method for removing a solvent according to claim 1, wherein the fluid is carbon dioxide.
範囲第１項記載の溶媒除去方法。3. The method for removing a solvent according to claim 1, wherein the chlorinated resin is chlorinated rubber.
１項記載の溶媒除去方法。4. The method for removing a solvent according to claim 1, wherein the solvent is carbon tetrachloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62192194A JPH0751607B2 (en) | 1987-03-27 | 1987-07-31 | Solvent removal method for chlorinated resin |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7344587 | 1987-03-27 | ||
| JP62-73445 | 1987-03-27 | ||
| JP62192194A JPH0751607B2 (en) | 1987-03-27 | 1987-07-31 | Solvent removal method for chlorinated resin |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JPH01102A JPH01102A (en) | 1989-01-05 |
| JPS64102A JPS64102A (en) | 1989-01-05 |
| JPH0751607B2 true JPH0751607B2 (en) | 1995-06-05 |
Family
ID=26414590
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62192194A Expired - Lifetime JPH0751607B2 (en) | 1987-03-27 | 1987-07-31 | Solvent removal method for chlorinated resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0751607B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6436605A (en) * | 1987-07-31 | 1989-02-07 | Asahi Denka Kogyo Kk | Removal of solvent from chlorinated polymer |
| US7790036B2 (en) | 2007-10-16 | 2010-09-07 | Yulex Corporation | Rapid expanded solvent extraction |
-
1987
- 1987-07-31 JP JP62192194A patent/JPH0751607B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS64102A (en) | 1989-01-05 |
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